US20260184655A1 · App 19/131,641
METHODS FOR PRODUCING OLEFINIC COMPOUNDS UTILIZNG REGENERATORS
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Application
Classifications
IPC Classifications
CPC Classifications
Applicants
Dow Global Technologies LLC
Inventors
Lin Luo, Hangyao Wang, Matthew T. Pretz, Quan Yuan, Liwei Li
Abstract
A method of producing olefinic compounds may include contacting a feed stream including one or more hydrocarbons with a particulate solid catalyst in a reactor. In the reactor, the one or more hydrocarbons may be dehydrogenated to form one or more products including one or more olefinic compounds and at least a portion of the particulate solid catalyst may be deactivated. The method may also include passing at least a portion of the deactivated particulate solid catalyst to a combustor. In the combustor, a supplemental fuel stream may enter the combustor through a supplemental fuel distributor and the supplemental fuel stream may be reacted to heat at least a portion of the deactivated particulate solid catalyst. The method may also include passing at least a portion of the heated deactivated particulate solid catalyst to an oxygen treatment zone to produce a reactivated particulate solid catalyst. The method may also include passing at least a portion of the reactivated particulate solid catalyst back to the combustor. In the combustor, the reactivated particulate solid catalyst may enter the combustor downstream of the supplemental fuel stream relative to a flow direction of the supplemental fuel steam and the deactivated particulate solid catalyst may enter the combustor upstream of the supplemental fuel stream relative to the flow direction of the supplemental fuel stream. The method may also include passing at least a portion of the reactivated particulate solid catalyst to the reactor.
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Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001]This application claims the benefit of U.S. Provisional Application Ser. No. 63/428,528 filed Nov. 29, 2022, the entire disclosure of which is hereby incorporated herein by reference.
TECHNICAL FIELD
[0002]Embodiments described herein generally relate to chemical processing and, more specifically, to processes and systems utilized for the production of olefinic compounds.
BACKGROUND
[0003]Olefinic compounds may be utilized as base materials to produce many types of goods and materials. For example, propylene may be utilized to manufacture polypropylene, propylene oxide, and acrylonitrile. Such products may be utilized in product packaging, chemical manufacturing, textiles, etc. Thus, there is an industry demand for olefinic compounds, such as ethylene, propylene, butene, and styrene, as well as processes to produce such materials.
SUMMARY
[0004]One method for producing olefinic compounds is by dehydrogenating hydrocarbons. In some embodiments, the dehydrogenation reaction may use a particulate solid such as, for example, a catalyst to promote the dehydrogenation reaction. Further, because of the endothermic nature of the dehydrogenation reaction, the reaction may also utilize an external heat source to promote the reaction. In such embodiments, the particulate solid may be passed to a combustor where a supplemental fuel is reacted to heat the particulate solid. The heated particulate solid may provide some or all of the heat utilized to continue the dehydrogenation reaction. However, reacting the supplemental fuel in the presence of the particulate solid may reduce the activity of the particulate solid in promoting the dehydrogenation reaction. Accordingly, it would be desired to limit the amount of particulate solid exposed to the supplemental fuel while still providing a sufficient heat source for the dehydrogenation reaction. The methods of the present disclosure may help limit the amount of particulate solid exposed to the supplemental fuel by passing both deactivated and reactivated particulate solid into the combustor in a particular distribution pattern. Specifically, embodiments described herein utilize methods whereby deactivated particulate solid catalyst is passed into the combustor upstream of the supplemental fuel, and whereby reactivated particulate solid catalyst is passed into the combustor downstream of the supplemental fuel. Such an arrangement may be beneficial by allowing for increased residence time for deactivated catalyst in the combustor, allowing more complete coke burn off, whereas regenerated catalyst recycled to the combustor generally includes less coke and can benefit from reduced residence time exposed to a supplemental fuel, which can deactivate the catalyst.
[0005]According to one or more embodiments of the present disclosure, a method of producing olefinic compounds may include contacting a feed stream including one or more hydrocarbons with a particulate solid catalyst in a reactor. In the reactor, the one or more hydrocarbons may be dehydrogenated to form one or more products including one or more olefinic compounds and at least a portion of the particulate solid catalyst may be deactivated. The method may also include passing at least a portion of the deactivated particulate solid catalyst to a combustor. In the combustor, a supplemental fuel stream may enter the combustor through a supplemental fuel distributor and the supplemental fuel stream may be reacted to heat at least a portion of the deactivated particulate solid catalyst. The method may also include passing at least a portion of the heated deactivated particulate solid catalyst to an oxygen treatment zone to produce a reactivated particulate solid catalyst. The method may also include passing at least a portion of the reactivated particulate solid catalyst back to the combustor. In the combustor, the reactivated particulate solid catalyst may enter the combustor downstream of the supplemental fuel stream relative to a flow direction of the supplemental fuel steam and the deactivated particulate solid catalyst may enter the combustor upstream of the supplemental fuel stream relative to the flow direction of the supplemental fuel stream. The method may also include passing at least a portion of the reactivated particulate solid catalyst to the reactor.
[0006]It is to be understood that both the preceding general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. Additional features and advantages of the embodiments will be set forth in the detailed description and, in part, will be readily apparent to persons of ordinary skill in the art from that description, which includes the accompanying drawings and claims, or recognized by practicing the described embodiments. The drawings are included to provide a further understanding of the embodiments and, together with the detailed description, serve to explain the principles and operations of the claimed subject matter. However, the embodiments depicted in the drawings are illustrative and exemplary in nature, and not intended to limit the claimed subject matter
BRIEF DESCRIPTION OF THE DRAWINGS
[0007]The following detailed description may be better understood when read in conjunction with the following drawings, in which:
[0008]
[0009]
[0010]When describing the simplified schematic illustrations of
[0011]Reference will now be made in greater detail to various embodiments, some of which are illustrated in the accompanying drawings.
DETAILED DESCRIPTION
[0012]Specific embodiments of the present application will now be described. The disclosure may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.
[0013]As described herein, methods for producing olefinic compounds may include reactivating a catalyst in a combustor by exposure to a supplemental fuel. In embodiments described herein, deactivated particulate solid catalyst and recycled reactivated particulate solid catalyst may be separately passed to the combustor in a different regions of the combustor. As described herein, “particulate solid catalysts” refer to particulate solids that may have catalytic functionality for dehydrogenation reactions and/or fuel combustion reactions. Where the term “particulate solid” is described herein, it may equally refer to a “particulate solid catalyst”.
[0014]Embodiments of the methods presently disclosed will now be described herein in detail in the context of the reactor system of
[0015]Now referring to
[0016]Generally, as is described herein, in embodiments illustrated in
[0017]The feed stream may enter feed inlet 434 into the reactor 202, and the product stream may exit the reactor system 103 via pipe 420. According to one or more embodiments, the reactor system 103 may be operated by feeding a chemical feed (e.g., in a feed stream) and a particulate solid into the upstream reactor section 254. The chemical feed contacts the particulate solid in the upstream reactor section 254, and each flow upwardly into and through the downstream reactor section 232 to produce a chemical product.
[0018]Now referring to
[0019]The upstream reactor section 254 may be connected to a transport riser 430, which, in operation may provide regenerated particulate solid in a feed stream to the reactor portion 206. The particulate solid entering the upstream reactor section 254 via transport riser 430 may be passed through line 424 to a transport riser 430, thus arriving from the regeneration unit 306. The particulate solid may come directly from the particulate solid separation section 216 via standpipe 422 and into the transport riser 430, where it enters the upstream reactor section 254. This particulate solid may be somewhat deactivated, but may still, in some embodiments, be suitable for reaction in the upstream reactor section 254, particularly when used in combination with the regenerated/reactivated particulate solid.
[0020]Still referring to
[0021]In one or more embodiments, the particulate solid may be capable of fluidization. In some embodiments, the particulate solid may exhibit properties known in the industry as “Geldart A” or “Geldart B” properties. Particles may be classified as “Group A” or “Group B” according to D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), 34-37; and D. Geldart, “Types of Gas Fluidization,” Powder Technol. 7 (1973) 285-292, which are incorporated herein by reference in their entireties.
[0022]Group A is understood by those skilled in the art as representing an aeratable powder, having a bubble-free range of fluidization; a high bed expansion; a slow and linear deaeration rate; bubble properties that may include a predominance of splitting/recoalescing bubbles, with a maximum bubble size and large wake; high levels of solids mixing and gas backmixing, assuming equal U-Umf (U is the velocity of the carrier gas, and Umf is the minimum fluidization velocity, typically though not necessarily measured in meters per second, m/s, i.e., there is excess gas velocity); axisymmetric slug properties; and no spouting, except in very shallow beds. The properties listed tend to improve as the mean particle size decreases, assuming equal cfp; or as the <45 micrometers (μm) proportion is increased; or as pressure, temperature, viscosity, and density of the gas increase. In general, the particles may exhibit a small mean particle size and/or low particle density (<1.4 grams per cubic centimeter, g/cm3), fluidize easily, with smooth fluidization at low gas velocities, and may exhibit controlled bubbling with small bubbles at higher gas velocities.
[0023]Group B is understood by those skilled in the art as representing a “sand-like” powder that starts bubbling at Umf; that exhibits moderate bed expansion; a fast deaeration; no limits on bubble size; moderate levels of solids mixing and gas backmixing, assuming equal U-Umf; both axisymmetric and asymmetric slugs; and spouting in only shallow beds. These properties tend to improve as mean particle size decreases, but particle size distribution and, with some uncertainty, pressure, temperature, viscosity, or density of gas seem to do little to improve them. In general, most of the particles having a particle size (cfp) of 40 μm<cfp<500 μm when the density (pp) is 1.4<pp<4 g/cm3, and preferably 60 μm<cfp<500 μm when the density (pp) is 4 g/cm3 and 250 μm<cfp<100 μm when the density (pp) is 1 g/cm3.
[0024]According to embodiments, the chemical product and the particulate solid may be passed out of the downstream reactor section 232 to a separation device 226 in the particulate solid separation section 216, where the particulate solid is separated from the chemical product, which is transported out of the particulate solid separation section 216. According to one or more embodiments, following separation from vapors in the separation device 226, the particulate solid may generally move through the strip zone 224 to the particulate solid outlet port 222 where the particulate solid is transferred out of the reactor portion 206 via line 426 and into the regeneration unit 306.
[0025]Now referring back to
[0026]Referring still to
[0027]Referring now to the regeneration unit 306, as depicted in
[0028]The particulate solid and flue gas produced in the combustor 350 may travel through riser 330 to the particulate solid separation section 316. In the particulate solid separation section 316 the flue gas and the particulate solid may be separated first by a riser termination separator 378 and then by a secondary separation device 326. As described in one or more embodiments, following separation of flue gas from the particulate solid in the riser termination separator 378 and secondary separation device 326, treatment of the processed particulate solid with an oxygen-containing gas is conducted in the oxygen treatment zone 312. In some embodiments, the oxygen treatment zone 312 includes a fluid solids contacting device. The fluid solids contacting device may include baffles or grid structures to facilitate contact of the processed catalyst with the oxygen-containing gas. Examples of fluid solid contacting devices are described in further detail in U.S. Pat. Nos. 9,827,543 and 9,815,040. The fluidization regime within the oxygen treatment zone may be bubbling bed type fluidization.
[0029]In one or more embodiments, the particulate solid may be exposed to the oxygen-containing gas in the oxygen treatment zone 312 for from 30 seconds to 20 minutes. For example, the particulate solid may be exposed to the oxygen-containing gas in the oxygen treatment zone 312 for from 30 seconds to 18 minutes, such as from 30 seconds to 16 minutes, from 30 seconds to 14 minutes, from 30 seconds to 12 minutes, from 30 seconds to 10 minutes, from 30 seconds to 8 minutes, from 30 seconds to 6 minutes, from 30 seconds to 4 minutes, from 30 seconds to 2 minutes, from 2 minutes to 20 minutes, from 2 minutes to 18 minutes, from 2 minutes to 16 minutes, from 2 minutes to 14 minutes, from 2 minute to 12 minutes, from 2 minutes to 10 minutes, from 2 minutes to 8 minutes, from 2 minutes to 6 minutes, from 2 minutes to 4 minutes, from 4 minutes to 20 minutes, from 4 minutes to 18 minutes, from 4 minutes to 16 minutes, from 4 minutes to 14 minutes, from 4 minutes to 12 minutes, from 4 minutes to 10 minutes, from 4 minutes to 8 minutes, from 4 minutes to 6 minutes, from 6 minutes to 20 minutes, from 6 minutes to 18 minutes, from 6 minutes to 16 minutes, from 6 minutes to 14 minutes, from 6 minutes to 12 minutes, from 6 minutes to 10 minutes, from 6 minutes to 8 minutes, from 8 minutes to 20 minutes, from 8 minutes to 18 minutes, from 8 minutes to 16 minutes, from 8 minutes to 14 minutes, from 8 minutes to 12 minutes, from 8 minutes to 10 minutes, from 10 minutes to 20 minutes, from 10 minutes to 18 minutes, from 10 minutes to 16 minutes, from 10 minutes to 14 minutes, from 10 minutes to 12 minutes, from 12 minutes to 20 minutes, from 12 minutes to 18 minutes, from 12 minutes to 16 minutes, from 12 minutes to 14 minutes, from 14 minutes to 20 minutes, from 14 minutes to 18 minutes, from 14 minutes to 16 minutes, from 16 minutes to 20 minutes, from 16 minutes to 18 minutes, or from 18 minutes to 20 minutes.
[0030]In one or more embodiments, a portion of the particulate solid may be passed through the oxygen treatment zone 312 and passed back to the reactor portion 206 via line 424. In one or more embodiments, a portion of the particulate solid may be passed through the oxygen treatment zone 312 and passed back to the combustor 350 via line 356 and pipe 428. Pipe 428 may separately carry the portion of particulate solid coming from the oxygen treatment zone 312 via line 356 and the portion of particulate solid coming from the particulate solid separation section 216 via line 426 to the particulate solids distributor 100, which may be operable to pass the two particulate solid portions separately into the combustor 350.
[0031]In one or more embodiments, at least a portion of the particulate solid may be removed from the oxygen treatment zone 312 after having passed through only part of the oxygen treatment zone. For example, if the oxygen treatment zone 312 exposed the particulate solid to the oxygen-containing gas for 5 minutes, then a portion of the particulate solid may be removed from the oxygen-treatment zone after having been exposed to the oxygen-containing gas for only 1 minute. In one or more embodiments, the portion of the particulate solid removed from the oxygen treatment zone 312 without having passed through the entire oxygen treatment zone 312 may be passed to the combustor 350 as reactivated particulate solid (not shown in
[0032]Referring now to
[0033]In one or more embodiments, a supplemental fuel stream may enter the combustor 350 through a supplemental fuel distributor 354. In one or more embodiments, the supplemental fuel stream may comprise hydrogen, methane, ethane, propane, natural gas, or combinations thereof. In the combustor 350, the supplemental fuel may react with oxygen and/or with the particulate solid. Without being bound by theory, it is believed that the combustion of the supplemental fuel in the combustor 350 may heat the particulate solid. However, it is also believed that contacting the particulate solid with the supplemental fuel stream may reduce the dehydrogenation activity of the particulate solid. Aside from the combustion of supplemental fuel, coke from the particulate solid may also combust in the combustor 350, which may heat the particulate solids and also reactivate the particulate solid.
[0034]Reactivated particulate solid 104 and deactivated particulate solid 105 (as described hereinafter) may enter the combustor 350 through a particulate solids distributor 100. Reactivated particulate solid 104 may be the portion of particulate solid passed to the combustor via line 356 from the oxygen treatment zone 312 of
[0035]As shown in
[0036]
[0037]As shown in
[0038]The reactivated particulate solid 104 may be passed into the inner conduit 200 through inner conduit inlet 210 and may pass through the inner conduit 200 and out inner conduit outlet 220 to the first solids director 240, which may direct the reactivated particulate solid 104 into the combustor 350. The deactivated particulate solid 105 may be passed into the outer conduit 300 through outer conduit inlet 310 and may pass through the outer conduit 300 and out outer conduit outlet 320 to the second solids director 340, which may direct the deactivated particulate solid 105 into the combustor 350.
[0039]Still referring to
[0040]Without being bound by theory, it is believed that by adding reactivated particulate solid 104 to the combustor 350 downstream of the supplemental fuel stream relative to a flow direction of the supplemental fuel stream and adding deactivated particulate solid 105 to the combustor 350 upstream of the supplemental fuel stream relative to the flow direction of the supplemental fuel stream the amount a particular particle of the particulate solid contacts the supplemental fuel may be reduced. It is believed that exposing the particulate solid to the supplemental fuel may reduce the dehydrogenation activity of the particulate solid and may reduce the stability of the particulate solid, which may shorten the lifespan of the particulate solid. It is believed that the heat produced by supplemental fuel combustion may heat particles of particulate solid nearer to the combustion to temperatures high enough to negatively affect the stability of the particulate solid, when compared to particles of particulate solid that are farther from the combustion of supplemental fuel. Accordingly, by adding the deactivated particulate solid 105 into the combustor at a positon upstream of the reactivated particulate solid 104 the deactivated particulate solid 104 may be exposed to more supplemental fuel combustion than reactivated particulate solid 104 such that the amount the reactivated particulate solid 104 is heated is reduced, improving the stability of the reactivated particulate solid 104 when compared to particulate solid exposed to more supplemental fuel combustion.
[0041]Without being bound by theory, it is also believed that because a portion of the reactivated particulate solid 104 may be passed back to the combustor 350, a particle of the reactivated particulate solid 104 may cycle through the combustor 350 multiple times before being passed to the reactor portion 206. Accordingly, if the reactivated particulate solid 104 is passed back to the combustor 350 in the same place as or further upstream of the deactivated particulate solid 105, a particle that has been through multiple combustion cycles may be exposed to more supplemental fuel combustion when compared to a particle that has been utilized in the methods of the present disclosure. As the deactivated particulate solid 105 is coming from the reactor portion 206, exposing the deactivated particulate solid 105 to the supplemental fuel stream into higher concentrations of supplemental fuel than the reactivated particulate solid 104 may reduce the amount of supplemental fuel combustion experienced by an individual particle of the particulate solid because the highest fuel concentration and thus combustion is experienced by particles that have been passed back to the reactor and then to the combustor and not by particles that have been repeatedly passed to the combustor from the oxygen treatment zone 312.
[0042]In one or more embodiments, the deactivated particulate solid 105 passed to the combustor 350 from the reactor portion 206 may have a temperature of from 580° C. to 800° C. For example, the deactivated particulate solid 105 passed to the combustor 350 from the reactor portion may have a temperature that is from 580° C. to 775° C., such as from 580° C. to 750° C., from 580° C. to 725° C., from 580° C. to 700° C., from 580° C. to 675° C., from 580° C. to 650° C., from 580° C. to 625° C., from 580° C. to 600° C., from 600° C. to 800° C., from 600° C. to 775° C., from 600° C. to 750° C., from 600° C. to 725° C., from 600° C. to 700° C., from 600° C. to 675° C., from 600° C. to 650° C., from 600° C. to 625° C., from 625° C. to 800° C., from 625° C. to 775° C., from 625° C. to 750° C., from 625° C. to 725° C., from 625° C. to 700° C., from 625° C. to 675° C., from 625° C. to 650° C., from 650° C. to 800° C., from 650° C. to 775° C., from 650° C. to 750° C., from 650° C. to 725° C., from 650° C. to 700° C., from 650° C. to 675° C., from 675° C. to 800° C., from 675° C. to 775° C., from 675° C. to 750° C., from 675° C. to 725° C., from 675° C. to 700° C., from 700° C. to 800° C., from 700° C. to 775° C., from 700° C. to 750° C., from 700° C. to 725° C., from 725° C. to 800° C., from 725° C. to 775° C., from 725° C. to 750° C., from 750° C. to 800° C., from 750° C. to 775° C., from 775° C. to 800° C., or any combination of these ranges.
[0043]In one or more embodiments, the reactivated particulate solid 104 passed to the combustor 350 from the oxygen treatment zone 312 may have a temperature of from 680° C. to 900° C. For example, the reactivated particulate solid passed 104 to the combustor 350 from the reactor portion may have a temperature that is from 680° C. to 875° C., such as from 680° C. to 850° C., from 680° C. to 825° C., from 680° C. to 800° C., from 680° C. to 775° C., from 680° C. to 750° C., from 680° C. to 725° C., from 680° C. to 700° C., from 700° C. to 900° C., from 700° C. to 875° C., from 700° C. to 850° C., from 700° C. to 825° C., from 700° C. to 800° C., from 700° C. to 775° C., from 700° C. to 750° C., from 700° C. to 725° C., from 725° C. to 900° C., from 725° C. to 875° C., from 725° C. to 850° C., from 725° C. to 825° C., from 725° C. to 800° C., from 725° C. to 775° C., from 725° C. to 750° C., from 750° C. to 900° C., from 750° C. to 875° C., from 750° C. to 850° C., from 750° C. to 825° C., from 750° C. to 800° C., from 750° C. to 775° C., from 775° C. to 900° C., from 775° C. to 875° C., from 775° C. to 850° C., from 775° C. to 825° C., from 775° C. to 800° C., from 800° C. to 900° C., from 800° C. to 875° C., from 800° C. to 850° C., from 800° C. to 825° C., from 825° C. to 900° C., from 825° C. to 875° C., from 825° C. to 850° C., from 850° C. to 900° C., from 850° C. to 875° C., from 875° C. to 900° C., or any combination of these ranges.
[0044]Combustion of supplemental fuel may heat the particulate solid. It is believed that because the heat transfer from one particle of particulate solid to another particle of particulate solid is rapid, the heat gained by combusting supplemental fuel may be transferred throughout the mass of particulate solid in the combustor without requiring every particle of particulate solid to be near the combustion of supplemental fuel. This may allow only a portion of the particulate solid to be directly exposed to the heat of supplemental fuel combustion while still heating the total mass of the particulate solid for use in the dehydrogenation reaction. Further, the reactivated particulate solid 104 may be hotter than the deactivated particulate solid 105 when the two portions of particulate solid enter the combustor 350, which means that it may be desired to heat the deactivated particulate solid 105 more than the reactivated particulate solid 104. Accordingly, exposing the deactivated particulate solid 105 to the supplemental fuel stream first may allow more fuel combustion to occur near the deactivated particulate solid 105 than near the reactivated particulate solid 104 heating the deactivated particulate solid 105 more than the reactivated particulate solid 104.
[0045]Without being bound by theory it is believed that by introducing the deactivated particulate solid 105 into the combustor 350 upstream of the supplemental fuel stream the deactivated particulate solid 105 may have a longer residence time in the combustor 350 than if it was introduced downstream of the supplemental fuel stream. This increased residence time in the combustor 350 may allow for a greater portion of coke to be removed from the deactivated particulate solid 105 when compared to a lower residence time in the combustor. It may be desired to remove as much of the coke that forms on the deactivated particulate solid 105 in the reactor portion 206 as possible to reactivate the deactivated particulate solid 105 and a longer residence time in the combustor 350 may remove more coke, when compared to a shorter residence time in the combustor 350.
[0046]As described herein, in one or more embodiments, an oxygen-containing gas may enter the combustor 350 through pipe 358 and lower gas distribution plate 352. In some embodiments, the oxygen in the oxygen-containing gas may react with coke that has formed on the particulate solid which may remove at least a portion of the coke from the particulate solid.
[0047]In non-limiting examples, the reactor system 103 described herein may be utilized to produce olefinic compounds from hydrocarbon feed streams. As used herein, the term “olefinic compounds” refers to hydrocarbons having one or more carbon-carbon double bonds apart from the formal double bonds in aromatic compounds. For example, ethylene and styrene are olefinic compounds, but ethylbenzene would not be an olefinic compound as the only double bonds present in ethylbenzene are formal double bonds present as part of the aromatic structure. Olefinic compounds may be produced from a variety of hydrocarbon feed streams by utilizing different reaction mechanisms. For example, olefinic compounds may be produced by at least dehydrogenation reactions, cracking reactions, dehydration reactions, and methanol-to-olefin reactions. These reaction types may utilize different feed streams and different particulate solid catalysts to produce olefinic compounds. It should be understood that when “catalysts” are referred to herein, they may equally refer to the particulate solid catalysts referenced with respect to the system of
[0048]According to one or more embodiments, the reaction may be a dehydrogenation reaction. According to such embodiments, the one or more hydrocarbons may be a hydrocarbon feed stream the hydrocarbon feed stream may comprise one or more of ethylbenzene, ethane, propane, n-butane, and i-butane. In one or more embodiments, the hydrocarbon feed stream may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of ethylbenzene. In one or more embodiments, the hydrocarbon feed stream may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of ethane. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of propane. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of n-butane. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of i-butane. In additional embodiments, the hydrocarbon feed stream may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. % or even at least 99 wt. % of the sum of ethylbenzene, ethane, propane, n-butane, and i-butane.
[0049]In one or more embodiments, the dehydrogenation reaction may utilize gallium and/or platinum particulate solids as a catalyst. In such embodiments, the particulate solids may comprise a gallium and/or platinum catalyst. As described herein, a gallium and/or platinum catalyst comprises gallium, platinum, or both. The gallium and/or platinum catalyst may be carried by an alumina or alumina silica support, and may optionally comprise potassium. Such gallium and/or platinum catalysts are disclosed in U.S. Pat. No. 8,669,406, which is incorporated herein by reference in its entirety. However, it should be understood that other suitable catalysts may be utilized to perform the dehydrogenation reaction.
[0050]In one or more embodiments, the reaction mechanism may be dehydrogenation followed by combustion (in the same chamber). In such embodiments, a dehydrogenation reaction may produce hydrogen as a byproduct, and an oxygen carrier material may contact the hydrogen and promote combustion of the hydrogen, forming water. Examples of such reaction mechanisms, which are contemplated as possible reactions mechanisms for the systems and methods described herein, are disclosed in WO 2020/046978 and U.S. Pat. Pub. No. 2021/0292259 the teachings of which are incorporated by reference in their entireties herein.
[0051]In one or more embodiments, the particulate solid catalyst may comprise an oxygen-carrier material and a dehydrogenation catalyst material. In some embodiments, the oxygen-carrier material and the dehydrogenation catalyst material may be separate particles of the particulate solid. In some embodiments, the oxygen-carrier material and the dehydrogenation catalyst may be contained in the same particles of the particulate solid.
[0052]In some embodiments, the particulate solid catalyst may comprise a “dual-purpose material” that may act as both a dehydrogenation catalyst as well as an oxygen-carrier material. It should be understood that, in at least the embodiments described herein where an oxygen-carrier material and a dehydrogenation catalyst are utilized in the same reaction vessel (such as those of
[0053]In one or more embodiments, the olefinic compounds may be present in a “product stream” sometimes called an “olefin-containing effluent”. Such a stream exits the reactor system of
[0054]In a first aspect of the present disclosure, a method of producing olefinic compounds may include contacting a feed stream including one or more hydrocarbons with a particulate solid catalyst in a reactor. In the reactor, the one or more hydrocarbons may be dehydrogenated to form one or more products including one or more olefinic compounds and at least a portion of the particulate solid catalyst may be deactivated. The method may also include passing at least a portion of the deactivated particulate solid catalyst to a combustor. In the combustor, a supplemental fuel stream may enter the combustor through a supplemental fuel distributor and the supplemental fuel stream may be reacted to heat at least a portion of the deactivated particulate solid catalyst. The method may also include passing at least a portion of the heated deactivated particulate solid catalyst to an oxygen treatment zone to produce a reactivated particulate solid catalyst. The method may also include passing at least a portion of the reactivated particulate solid catalyst back to the combustor. In the combustor, the reactivated particulate solid catalyst may enter the combustor downstream of the supplemental fuel stream relative to a flow direction of the supplemental fuel steam and the deactivated particulate solid catalyst may enter the combustor upstream of the supplemental fuel stream relative to the flow direction of the supplemental fuel stream. The method may also include passing at least a portion of the reactivated particulate solid catalyst to the reactor.
[0055]A second aspect of the present disclosure includes any previous aspect or combination of aspects, where the reactivated particulate solid catalyst and the deactivated particulate solid catalyst are passed to the combustor through a particulate solids distributor that separately passes the reactivated particulate solid catalyst and deactivated particulate solid catalyst into the combustor.
[0056]A third aspect of the present disclosure includes any previous aspect or combination of aspects, where the particulate solids distributor extends into the reactor through a bottom end of the reactor.
[0057]A fourth aspect of the present disclosure includes any previous aspect or combination of aspects, where the particulate solids distributor passes the reactivated particulate solid catalyst into the combustor above the supplemental fuel distributor and passes the deactivated particulate solid catalyst into the combustor below the supplemental fuel distributor.
[0058]A fifth aspect of the present disclosure includes any previous aspect or combination of aspects, where the combustor operates as a fast fluidized, turbulent, or bubbling bed.
[0059]A sixth aspect of the present disclosure includes any previous aspect or combination of aspects, where the temperature of the deactivated particulate solid catalyst passed to the combustor is from 580° C. to 800° C.
[0060]A seventh aspect of the present disclosure includes any previous aspect or combination of aspects, where the temperature of the reactivated particulate solid catalyst passed to the combustor is from 680° C. to 900° C.
[0061]An eighth aspect of the present disclosure includes any previous aspect or combination of aspects, where in the oxygen treatment zone the heated deactivated catalyst is exposed to an oxygen-containing gas
[0062]A ninth aspect of the present disclosure includes any previous aspect or combination of aspects, where the heated deactivated particulate solid catalyst is exposed to the oxygen-containing gas for from 30 seconds to 20 minutes.
[0063]A tenth aspect of the present disclosure includes any previous aspect or combination of aspects, where the particulate solid catalyst comprises one or both of a dehydrogenation catalyst material and an oxygen-carrier material.
[0064]An eleventh aspect of the present disclosure includes any previous aspect or combination of aspects, where the dehydrogenation catalyst material and the oxygen-carrier material are contained in the same particles of the particulate solid catalyst.
[0065]A twelfth aspect of the present disclosure includes any previous aspect or combination of aspects, where the supplemental fuel stream comprises hydrogen, methane, ethane, propane, natural gas or combinations thereof.
[0066]A thirteenth aspect of the present disclosure includes any previous aspect or combination of aspects, where coke forms on the deactivated particulate solid catalyst in the reactor and at least a portion of the coke on the deactivated particulate solid catalyst is reacted in the combustor.
[0067]A fourteenth aspect of the present disclosure includes any previous aspect or combination of aspects, where the particulate solid catalyst is a Geldart A or Geldart B particulate.
[0068]A fifteenth aspect of the present disclosure includes any previous aspect or combination of aspects, where the one or more hydrocarbons comprise propane and the one or more olefinic compounds comprise propylene.
[0069]It will be apparent to those skilled in the art that various modifications and variations can be made to the presently disclosed technology without departing from the spirit and scope of the technology. Since modifications combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the presently disclosed technology may occur to persons skilled in the art, the technology should be construed to include everything within the scope of the appended claims and their equivalents. Additionally, although some aspects of the present disclosure may be identified herein as preferred or particularly advantageous, it is contemplated that the present disclosure is not limited to these aspects.
[0070]It is noted that the various details described in this disclosure should not be taken to imply that these details relate to elements that are essential components of the various embodiments described in this disclosure, even in cases where a particular element is illustrated in each of the drawings that accompany the present description. Unless specifically identified as such, no feature disclosed and described herein should be construed as “essential”. Contemplated embodiments of the present technology include those that include some or all of the features of the appended claims.
[0071]For the purposes of describing and defining the present disclosure it is noted that the term “about” are utilized in this disclosure to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The term “about” are also utilized in this disclosure to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.
[0072]In relevant cases, where a composition is described as “comprising” one or more elements, embodiments of that composition “consisting of” or “consisting essentially of” those one or more elements is contemplated herein.
[0073]It should be appreciated that compositional ranges of a chemical constituent in a stream or in a reactor should be appreciated as containing, in some embodiments, a mixture of isomers of that constituent. For example, a compositional range specifying butene may include a mixture of various isomers of butene. It should be appreciated that the examples supply compositional ranges for various streams, and that the total amount of isomers of a particular chemical composition can constitute a range.
[0074]It is noted that one or more of the following claims and the detailed description utilize the terms “where” or “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”
[0075]It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. Where multiple ranges for a quantitative value are provided, these ranges may be combined to form a broader range, which is contemplated in the embodiments described herein.
[0076]As would be understood in the context of the term as used herein, the term “passing” may include directly passing a substance between two portions of the disclosed system and, in some other instances, to mean indirectly passing a substance between two portions of the disclosed system. For example, indirect passing may include steps where the named substance passes through an intermediate operations unit, valve, sensor, etc.
Claims
1. A method for producing olefinic compounds, the method comprising:
contacting a feed stream comprising one or more hydrocarbons with a particulate solid catalyst in a reactor, wherein in the reactor:
the one or more hydrocarbons are dehydrogenated to form one or more products comprising one or more olefinic compounds; and
at least a portion of the particulate solid catalyst is deactivated;
passing at least a portion of the deactivated particulate solid catalyst to a combustor, wherein in the combustor:
a supplemental fuel stream enters the combustor through a supplemental fuel distributor; and
the supplemental fuel stream is combusted to heat at least a portion of the particulate solid catalyst;
passing at least a portion of the heated deactivated particulate solid catalyst to an oxygen-treatment zone to produce a reactivated particulate solid catalyst;
passing at least a portion of the reactivated particulate solid catalyst back to the combustor, wherein the reactivated particulate solid catalyst enters the combustor downstream of the supplemental fuel stream relative to a flow direction of the supplemental fuel stream and the deactivated particulate solid catalyst enters the combustor upstream of the supplemental fuel stream relative to the flow direction of the supplemental fuel stream; and
passing at least a portion of the reactivated particulate solid catalyst to the reactor.
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